Methods of combatting fungi and bacteria using substituted-alpha isonitrosi-acetophenones

ABSTRACT

Novel biocide compositions having as the active compound an acetophenone of the formula   WHEREIN R is hydrogen, hydroxy and methyl and a method of killing bacteria and fungi.

United States Patent Perronnet et al.

[4 Nov. 18, 1975 METHODS OF 'COMBATTING FUNGI AND BACTERIA USING SUBSTITUTED-ALPHA ISONlTROSI-ACETOPHENONES Inventors: Jacques Perronnet; Pierre Girault,

both of Paris, France Assignee: Roussel Uclaf, Paris, France Filed: Dec. 10, 1973 Appl. No.: 423,211

Foreign Application Priority Data Dec 27, 1972 France 72.46323 References Cited UNITED STATES PATENTS 2/1974 Bertin et a1. 424/311 X Primary Examiner.1erome D. Goldberg Assistant Eramz'rier-Allen J. Robinson Attorney, Agent, or FirmHammond & Littell [5 7 ABSTRACT Novel biocide compositions having as the active compound an acetophenone of the formula wherein R is hydrogen, hydroxy and methyl and a method of killing bacteria and fungi.

4 Claims, No Drawings METHODS'OF COMBATTINC FUNGI-AND BACTERIA usmc SUBSTITUTED-ALPHA ISONITROSI-ACETOPHENONES OBJECTS OF THE INVENTION It is an object of the invention to provide novel biocidal compositions.

It is another object of the invention to provide a novel method of killing bacteria and combatting fungi.

These and other objects and advantages of the invention will become obvious from the following detailed description.

' THE INVENTION The novel biocidal compositions of the invention are comprised of a biocidally effective amount of at least one compound of formula I and preferably a carrier,

The compositions may also contain one or more other pesticidal agents. The biocidal compositions of the invention have remarkable bactericidal and germicidal properties which make them useful as industrial biocides for combatting fungi and bacteria which develop in aqueous or non-aqueous media used for the production of diverse industrial products. They are particularly useful for preventing and eliminating bacterial slime in paper-making circuits or in treatment of hides, vegetable tanning liquors, and leathers or in paints, lacquers, glues, ink and lubricating oils.

Suitable compounds of formula I are m-bro'mo-wisonitroso-acetophe none described by Sassenberg [Ann., Vol. 594 (1955), p. 185], w-bromo-w-isonitroso-4-hydroxyacetophenone described by Perti. et al. [Indian J. Chem., Vol. 5 (12) (1967), p. 622] and bromo-m-isonitroso-4-methylacetophenone described by Perti et al. [Proc. Natl. Acad. Sci. India, Vol. 29 pt 3 (1960), p 287].

The compositions may also be incorporated into cosmetic soaps whose yield is capable of preventing the inconveniences caused by the presence of germs, particularly the bacteria on the surface of the human body.

The m-bromo-m-isonitroso-acetophenones may be used to combat Aerobacter aerogenes, Pseudomonas aeruginosa, Serratia marcescens, Bacillus sublilis, Staphylococcus aureus, Escherichia coli, Flavobacterium aquaweight of Zeosil 39 (a precipitated synthetic hydrated 2 can beprepared by grinding the active compound with an inert solid or by impregnation of a solid support with .a solution of the active compound in a solvent which is next evaporated.

A typical biocidal composition of the invention consists of a wettable powder containing 25 percent by weight of w-bromo-w-isonitroso-4-hydroxy acetophenone of formula I, 15 percent by weight of Ekapersol S (a condensation product of sodium naphthalene sulfonate), 0.5 percent by weight of Brecolane N.V.A. (sodium alkylnaphthalene sulfonate), 34.5 percent by silica) and 25 percent by weight of Vercoryl S (colloidal Kaolin).

The novel method of the invention for combatting bacteria and fungi comprises contacting bacteria and fungi witha lethal amount of the acetophenones of formula I. The method is particularly useful for preventing the pollution of industrial waters such as aqueous waters in paper-making which may also contain sizing resins. In particular, the novel biocidal method comprise contacting bacteria and fungi with a biocidal amount of the acetophenone compounds of formula I and preferably preventing bacterial slime in aqueous media comprising incorporating a bactericidal amount of the acetophenone compounds of formula I in an aqueous media.

Tests effected in the presence of material such as paper pulp in aqueous suspension with resin sizing in conditions analogous to those used in practice demonstrates the biocidal properties of the acetophenone' compounds of formula I.

The compounds of formula I may be prepared by reacting-aluminum bromide and acetyl bromide with a compound of the formula wherein R has the above definition or by reacting alkyl nitrite in the presence of hydrochloric acid with the correspondingm-bromo-acetophenone or by reacting an alkali metal bromide and hydrobromic acid with a compound of the formula O C-C=NOH III I Cl wherein R has the above definition. The last reaction is preferably effected in an organic solvent such as methanol,ethanol, propanol or isopropanol and the reaction is more complete when terminated bromic gas.

w-chloro-w-isonitroso-acetophenones of the formula by bubbling hydroare known biocides and these compounds. as well as the compounds of formula 1. liberate in aqueous media small amounts of the hydracid. namely hydrochloric acid and hydrobromic acid respectively. In order to re- STUDY OF THE BACTERICIDAL ACTIVITY The inhibition of bacteria tested cultivated on a paper pulp madium enriched in bacteria showed the biduce attack of certain industrial apparatus such as 5 ocidal efficacy of w-bromo-w-isonitroso-acetophenone pumps in which the biocides come in contact, it is more (compound A) and w-bromo-w-isonitroso-4-hydroxadvantageous to use the products of formula I which yacetophenone (compound B). The test used 12.5 liberate hydrobromic acid rather than hydrochloric gm/liter of paper pulp in an aqueous suspension with acid. resin sizing and the contamination was effected with a 1n the following example there is described a pre bacterial suspension of Aerobacter aerogenes. The test ferred embodiment to illustrate the invention. Howcompounds were added at concentrations of 50, 25, ever, it should be understood that the invention is'not 12.5. 6.25. and 3.125 ppm and the suspensions were intended to be limited to the specific embodiment. incubated at 37C. The number of germs in each test was determined before and 45 mn, four and seven EXAMPLE 1 hours after the addition of the test compound. w-bromo-w-isonitroso-acetophenone Petri dishes containing a gelled medium thus were g of Chloro w isonitroso acetophenone and 20 seeded and were incubated at 37C for 48 hours. The g of sodium bromide were added to a solution of 51 g number then was determined T rgsults are of hydrogen bromide gas in 200 m] of ethanol and the 70 expressed in percentage of corrected anti-bacterial efmixture was stirred for 17 hours at room temperature. 5 fecuvenes (CE) of the product to be tested as Conl- The insolubles were removed by filtration and the filpared the Qlmested conlrols The cofmted anutrate was distilled to dryness under reduced pressure. bacterial effectiveness (CE) 15 calculated in the follow- The residue was dissolved in tetrahydrofuran and the mg Way: solution was treated with activated carbon, stirred and filtered. The filtrate was distilled to dryness under re- CE: decrease in specifmn increase A 00 duced pressure and the residue was added to methylene mmrol chloride. The solution was cooled and the precipitate TABLE 1 Products Compound A Compound B m M.A. 50 25 12.5 6.25 3.125 50 25 12.5 6.25 3.125 tlme The results of Table I show that compounds A and B possess an high biocidal activity in the test.

Various modifications of the compositions and method of the invention may be made without departing from the spirit or scope thereof and it is to be understood that the invention is to be limited only as deformed was recovered by vacuum filtrat1on. was 45 fined in the pp claims. washed and dr1ed to obta n 15.5 g of w-bromo-w-tsoniwe claim: troso'acetophenone meltmg at 137C 1. A method of combatting bacteria and fungi com- EXAMPLE 2 prising contacting bacteria and fungi with a lethal amount of a bactericidal and fungicidal compound of w-bromo w-isonitroso 4-hydr0xy acetophenone the formula 10 g of w-bromo-w-isonitroso-acetophenone and 10 g of sodium bromide were added to 120 ml of an ethanol 0 solution containing 17 g of hydrobromide gas per 100 LL ml and the mixture was stirred for 36 hours in a closed R -C=NOH container. The insolubles were removed by filtration I and after cooling to 10C, hydrobromide gas was bub- Br bled through the solution for 1 hour. The mixture was distilled to dryness under reduced pressure and the reswherein R is selected from the group consisting of hyidue was taken up in tetrahydrofuran. The solution was drogen, hydroxy and methyl. treated with activated carbon, stirred and filtered. The 2. The method of claim 1 wherein the bacteria and filtrate was evaporated to dryness and the residue was fungi are in industrial water and the bactericidal and added to methylene chloride. The solution was cooled fungicidal compound is added thereto. to 0C and the precipitate formed was obtained by vac- 3. The method of claim 1 wherein R is hydrogen. uum filtration and was dried to obtain 7 g of w-bromo- 4. The method of claim 1 wherein R is hydroxy.

w-isonitroso-4-hydroxyacetophenone melting at C. 

2. The method of claim 1 wherein the bacteria and fungi are in industrial water and the bactericidal and fungicidal compound is added thereto.
 3. The method of claim 1 wherein R is hydrogen.
 4. The method of claim 1 wherein R is hydroxy. 